KR102206266B1 - Functional resin composition using biomass resources - Google Patents

Abstract

The present invention relates to a functional resin composition using a biomass-derived component, and more specifically, a biomass-derived component, an aromatic dicarboxylic acid, an alcohol mixture, a chain extender and a polyfunctional compound, and the biomass-derived component Is composed of biomass-derived succinic acid alone or a mixture of biomass-derived succinic acid and fossil-derived aliphatic dicarboxylic acid.
The functional resin composition composed of the above components exhibits excellent processability, tear strength, tensile strength, and hydrolysis resistance, and thus exhibits an effect of suppressing changes over time.

Description

Functional resin composition using biomass-derived ingredients {FUNCTIONAL RESIN COMPOSITION USING BIOMASS RESOURCES}

The present invention relates to a functional resin composition using a biomass-derived component, and more particularly, a biomass-derived component that exhibits an effect of suppressing changes over time due to excellent process formability, tear strength, tensile strength and hydrolysis resistance. It relates to a functional resin composition.

Synthetic resins can be mass-produced in a variety of ways, and have excellent light weight, durability, price competitiveness, chemical resistance and mechanical properties, and are widely used in human life in modern life as well as food, pharmaceuticals, agricultural packaging, and industrial packaging. have.

However, these synthetic resin materials are disposed of through a process such as landfill or incineration after use.In the case of landfill, it takes a very long time for the synthetic resin material to decompose in the ground, and in the case of incineration, harmful gases such as dioxin are generated. There was this.

Environmental pollution caused by synthetic resins is currently reaching a level of concern worldwide, and biodegradable resins are being actively developed as one of the means to solve these problems.

Biodegradable resin is a resin that is finally decomposed into water and carbon dioxide by microorganisms in soil or water. The biodegradable resin developed so far is polylactic acid (PLA) synthesized by ring-opening reaction of lactic acid or lactide in the presence of a chemical catalyst or enzyme. , Polycaprolactone and diol-dicarboxylic acid-based aliphatic polyesters synthesized chemically starting from epsilon caprolactone monomers, and polyhydroxybutyrate (PHB) prepared by in vivo synthesis of other microorganisms, among which The most representative material is an aliphatic (or aliphatic/aromatic) polyester obtained by polymerization of polylactic acid (PLA) and diols and dicarboxylic acids.

Among them, polylactic acid is the most environmentally friendly product derived from biomass resources, but its use is limited due to its physical properties such as low heat resistance, strong brittleness, and a slow biodegradation rate.

On the other hand, unlike this, the aliphatic (or aliphatic/aromatic) polyester produced from diol and dicarboxylic acid exhibits similar properties to polyethylene and polypropylene, and is therefore expected as an alternative resource for synthetic resins.

However, the biodegradable polyester resins using the biomass-derived raw materials have a lower degree of completion of the reaction due to impurities contained in the biomass-derived raw materials and are more easily hydrolyzed than the fossil-derived polyesters, resulting in reduced durability. There was a problem.

Korean Patent Registration No. 10-0722516 (2007.05.21.) Korean Patent Publication No. 10-2013-0118221 (2013.10.29.) Korean Patent Registration No. 10-1276100 (2013.06.12.)

It is an object of the present invention to provide a functional resin composition using a biomass-derived component that exhibits an effect of suppressing changes over time due to excellent process formability, tear strength, tensile strength and hydrolysis resistance.

An object of the present invention is composed of a biomass-derived component, an alcohol mixture, a chain extender, and a multifunctional compound, and the biomass-derived component comprises biomass-derived succinic acid alone or biomass-derived succinic acid and fossil-derived aliphatic dicarboxylic acid. It is achieved by providing a functional resin composition using a biomass-derived component, characterized in that it consists of a mixture.

According to a preferred feature of the present invention, the aliphatic dicarboxylic acid derived from fossil raw materials is from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, and anhydrides thereof. It shall consist of one or more selected.

According to a more preferred feature of the present invention, the alcohol mixture is composed of at least one selected from the group consisting of biomass-derived 1,4-butanediol and fossil-derived aliphatic diols.

According to a more preferred feature of the present invention, the fossil-derived aliphatic diol is ethylene glycol, 1,3-propanediol, neopentyl glycol, propylene glycol, 1,2-butanediol, 1,4-butanediol, and 1,6-hexane. It consists of at least one selected from the group consisting of diols.

According to a further preferred feature of the present invention, the chain extender is made of an isocyanate compound or a carbodiimide compound.

According to an even more preferred feature of the present invention, the polyfunctional compound is to be prepared through an esterification reaction of 4,4-bis(4-hydroxyphenyl)valeric acid and polyethylene glycol as shown in [Chemical Formula 1] below.

[Formula 1]

Here, n is an integer of 8 to 10.

According to a further preferred feature of the present invention, the polyfunctional compound is prepared by esterification of DL-malic acid and 1,4-cyclohexanedimethanol in a nitrogen atmosphere as shown in [Chemical Formula 2] below.

[Formula 2]

Here, X is an integer of 3 to 5.

According to an even more preferred feature of the present invention, the functional resin composition using the biomass-derived component may further include an aromatic dicarboxylic acid. The aromatic dicarboxylic acid is composed of at least one selected from the group consisting of dimethyl terephthalate, terephthalic acid, isophthalic acid, and naphthoic acid.

The functional resin composition using the biomass-derived component according to the present invention has excellent processability, tear strength, tensile strength, and hydrolysis resistance, and thus exhibits an excellent effect of providing a functional resin that suppresses changes over time.

Hereinafter, a preferred embodiment of the present invention and the physical properties of each component will be described in detail, but this is for explaining in detail enough that one of ordinary skill in the art can easily implement the invention, This does not mean that the technical spirit and scope of the present invention are limited.

The functional resin composition using the biomass-derived component according to the present invention comprises a biomass-derived component, an alcohol mixture, a chain extender, and a multifunctional compound.

In addition, the functional resin composition using the biomass-derived component according to the present invention further comprises an aromatic dicarboxylic acid in addition to the biomass-derived component, an alcohol mixture, a chain extender, and a polyfunctional compound.

The biomass-derived component is composed of biomass-derived succinic acid alone or a mixture of biomass-derived succinic acid and fossil-derived aliphatic dicarboxylic acid, and the fossil-derived aliphatic dicarboxylic acid mixture is oxalic acid, malonic acid, succinic acid, and glue. It is preferably composed of at least one selected from the group consisting of taric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, and anhydrides thereof.

Biomass-derived succinic acid, an essential component used in the present invention, is used to enhance the eco-friendliness of aliphatic and aromatic copolyesters produced from conventional fossil resources, and substances such as starch and cellulose obtained through photosynthesis by plants It is obtained through fermentation, extraction, purification, etc. In the present invention, commercialized products originating from plant resources as described above can be used without special post-treatment.

In addition, the aliphatic dicarboxylic acid derived from the fossil material preferably has 0 to 8 carbon atoms, and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid and anhydrides thereof More preferably, it is made of at least one selected from the group consisting of.

The alcohol mixture is composed of at least one selected from the group consisting of biomass-derived 1,4-butanediol and fossil-derived aliphatic diol, and the fossil-derived aliphatic diol is ethylene glycol, 1,3-propanediol, neopentyl glycol, It is preferably composed of at least one selected from the group consisting of propylene glycol, 1,2-butanediol, 1,4-butanediol, and 1,6-hexanediol.

The chain extender is made of an isocyanate compound or a carbodiimide compound, and the isocyanate compound is 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4-diphenylmethane diisocyanate, and 2,2-diphenyl It is preferable to consist of one selected from the group consisting of methane diisocyanate,

The carbodiimide compound is 1,3-dicyclohexylcarbodiimide, HMV-8CA, HMV-10B sold by Nisshinbo, STABILIZER 9000 from Raschig, STABILIZER 7000, bis-(2,6-diisopropyl-phenyl) Lin-2,4-carbodiimide) and poly-(1,3,5-triisopropyl-phenylly-2,4-carbodiimide) is preferably composed of one selected from the group consisting of.

The aromatic dicarboxylic acid, which is a component that may be further included, is preferably composed of at least one selected from the group consisting of dimethyl terephthalate, terephthalic acid, isophthalic acid and naphthoic acid.

The polyfunctional compound is prepared through an esterification reaction of 4,4-bis(4-hydroxyphenyl)valeric acid and polyethylene glycol as shown in [Chemical Formula 1] below, or

[Formula 1]

(Where n is an integer from 8 to 10.)

As shown in [Chemical Formula 2] below, it is preferable to use DL-malic acid and 1,4-cyclohexanedimethanol prepared through an esterification reaction in a nitrogen atmosphere.

[Formula 2]

(Where, X is an integer of 3 to 5.)

The polyfunctional compound prepared through the esterification reaction of 4,4-bis(4-hydroxyphenyl)valeric acid and polyethylene glycol as shown in Chemical Formula 1 is 4.4-bis(4-hydroxyphenyl)valeric acid in the presence of a catalyst. An acid and polyethylene glycol having an average molecular weight of 400 are prepared by performing an esterification reaction at 210° C. for 2 hours, and the process of generating a polyfunctional compound having the structure as in Formula 1 is shown in Scheme 1 below.

[Scheme 1]

(Where n is an integer from 8 to 10.)

The polyfunctional compound having the structure of Formula 1 prepared through the same process as in Reaction Scheme 1 is introduced into the esterification step between the aliphatic dicarboxylic acid and the aliphatic diol when synthesizing the product aliphatic and aromatic copolyesters. By improving the esterification reactivity between succinic acid and aliphatic diol derived from inferior biomass, the reaction rate and molecular weight increase smoothly, resulting in productivity and excellent mechanical properties, as well as improving hydrolysis resistance by finely connecting the synthesized polymer chain structure. It serves to provide a resin composition having excellent durability.

In addition, the polyfunctional compound having the structure of Formula 1 can be used as a reaction aid to solve the problems of long reaction time, weak mechanical properties, and rapid change over time due to impurities contained in the biomass-derived succinic acid.

The resin composition prepared by using the polyfunctional compound having the structure of Formula 1 above has a number average molecular weight of 40,000 to 100,000, a molecular weight distribution of 2.0 to 3.8, a melt flow index of 190°C, and 1g/10min to 20g under the conditions of 2,160kg It exhibits a characteristic of /10min and a melting point of 95°C to 170°C.

In addition, since the polyfunctional compound having the structure as in Formula 2 improves the reaction rate and molecular weight of the resin composition, it provides a resin composition having excellent mechanical properties and storage stability.

The resin composition prepared by using the polyfunctional compound having the structure of Formula 2 above has a number average molecular weight of 40,000 to 100,000, a molecular weight distribution of 2.0 to 3.8, a melt flow index of 190°C, and 1g/10min to 20g under the conditions of 2,160kg It exhibits a characteristic of /10min and a melting point of 95°C to 170°C.

In particular, polyfunctional monomers such as glycerol and citric acid, which are branching agents commonly used in polyester production, have difficulty in controlling the reaction, making it difficult to obtain a uniform resin composition, and a high defect rate due to gelation of the resin, but has a structure like the above formula (2). The polyfunctional compound shown has a difference in the reaction activity of the functional groups and has a long chain, so the conditions for use are not difficult compared to the polyfunctional monomer due to steric hindrance in the reaction, and the usable range is also wide. In addition, the long-chain polyfunctional compound is introduced at the initial stage of the esterification reaction when synthesizing an aliphatic copolyester or aliphatic/aromatic copolyester to accelerate the bonding between the polymer chains to quickly increase the molecular weight of the reactant, as well as the resulting resin composition. It plays a role in improving the processability of the obtained resin composition by widening the molecular weight distribution by creating a side branch in the molecular main chain of

In addition, it serves to improve the tear strength and elongation rate and biodegradability of the final resin composition by forming a side branch and having a ring structure in the polymer structure of the resin composition to be produced.

Hereinafter, a method for preparing a functional resin composition using a biomass-derived component according to the present invention and physical properties of the resin composition prepared through the method will be described with reference to examples.

<Production Example 1>

A 1L round-bottom flask was replaced with nitrogen, 4.4-bis(4-hydroxyphenyl)valeric acid 286.33g, polyethylene glycol 440g with an average molecular weight of 400, and monobutyltin oxide 0.01g as a catalyst were added at 210℃ for 2 hours. During the esterification reaction, water, which is a by-product of the reaction, was sufficiently discharged to prepare a polyfunctional compound having the structure of Formula 1 below.

[Formula 1]

(Where n is an integer from 8 to 10.)

<Production Example 2>

A 1 L round bottom flask was replaced with nitrogen, and 134.09 g of DL-malic acid, 173.05 g of 1,4-cyclohexanedimethanol and 0.1 g of titanium isopropoxide as a catalyst were added thereto, followed by esterification at 210° C. for 120 minutes. A polyfunctional compound having the structure of the following formula (2) was prepared by sufficiently distilling 2 moles of the theoretical amount of water, which is a by-product of the reaction, with respect to 1 mole of DL-malic acid introduced by the reaction.

[Formula 2]

(Where, X is an integer of 3 to 5.)

<Example 1>

A 100 L reactor was replaced with nitrogen, and 19.42 kg of dimethyl terephthalate and 23.43 kg of 1,4-butanediol were added to the reactor, and the reaction temperature was fixed at 200° C., and the esterification was carried out for two hours to drain methanol. At this time, 10 g of tetrabutyl titanate was added as a catalyst, and 10 g of trimethyl phosphate was added as a stabilizer. After the theoretical amount of methanol was spilled, 22.44 kg of succinic acid derived from biomass resources (the Netherlands, Reverdia's biosuccinium) and 15 g of the multifunctional compound prepared in Preparation Example 1 were added, and the reaction temperature was fixed at 200°C and water was drained. Made it. At this time, 10 g of dibutyl tin oxide, 10 g of tetrabutyl titanate, and 20 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was continuously raised, 10 g of antimony trioxide was added as a catalyst, and condensation polymerization was carried out for 130 minutes under a reduced pressure of 1.5 torr at a temperature of 243°C, and 10 kg of the reactant obtained through the condensation polymerization reaction 50 g of 1,6-hexamethylene diisocyanate was mixed and a chain extension reaction was carried out at 125°C with a twin screw extruder having a diameter of 58 mm to prepare a functional resin composition using a biomass-derived component.

<Example 2>

Proceed in the same manner as in Example 1, but a functional resin composition using a biomass-derived component was prepared by using the multifunctional compound prepared through Preparation Example 2.

<Example 3>

A 100 L reactor was replaced with nitrogen, and 18.64 kg of dimethyl terephthalate and 23.43 kg of 1,4-butanediol were added to the reactor, and the reaction temperature was fixed at 200° C., and the esterification was carried out for two hours to discharge methanol. At this time, 10 g of tetrabutyl titanate was added as a catalyst, and 10 g of trimethyl phosphate was added as a stabilizer. After the theoretical amount of methanol was spilled, 12.28 kg of succinic acid derived from biomass resources (the Netherlands, Reverdia's biosuccinium) and 10 g of the multifunctional compound prepared in Preparation Example 1 were added, and the reaction temperature was fixed at 200°C and water was drained. Made it. At this time, 10 g of dibutyl tin oxide, 10 g of tetrabutyl titanate, and 20 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was continuously increased, 10 g of antimony trioxide was added as a catalyst, and a condensation polymerization reaction was carried out for 162 minutes under a reduced pressure of 1.5 torr at a temperature of 243°C, and 10 kg of the reaction product obtained through the condensation polymerization reaction Ebis-(2,6-diisopropyl-phenylline-2,4-carbodiimide) 25g was mixed and chain extension reaction was carried out at 120℃ with a twin screw extruder with a diameter of 58mm. A functional resin composition was prepared.

<Example 4>

Proceed in the same manner as in Example 3, but a functional resin composition using a biomass-derived component was prepared by using the multifunctional compound prepared through Preparation Example 2.

<Example 5>

A 100 L reactor was replaced with nitrogen, and 23.62 kg of succinic acid derived from biomass resources (the Netherlands, Reverdia's biosuccinium) and 23.43 kg of 1,4-butanediol derived from biomass resources (Myriant Bio-BDO, USA) were added to the reactor, and the above Preparation Example 1 After adding 18 g of the polyfunctional compound prepared through the method, the reaction temperature was fixed at 200° C. and water was discharged. At this time, as a catalyst, 5 g of dibutyl tin oxide, 15 g of tetrabutyl titanate, and 15 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was continuously increased, 15 g of antimony trioxide was added as a catalyst, and condensation polymerization was carried out for 170 minutes under a reduced pressure of 1.5 torr at a temperature of 243°C, and 10 kg of the reaction product obtained through the condensation polymerization reaction Mixing 45 g of 1,6-hexamethylene diisocyanate and performing a chain extension reaction at a temperature of 120° C. with a twin screw extruder having a diameter of 58 mm to prepare a functional resin composition using a biomass-derived component.

<Example 6>

Proceed in the same manner as in Example 5, but a functional resin composition using a biomass-derived component was prepared using the multifunctional compound prepared through Preparation Example 2.

<Example 7>

A 100 L reactor was replaced with nitrogen, and 23.3 kg of dimethyl terephthalate and 22.53 kg of 1,4-butanediol derived from biomass resources (Myriant Bio-BDO, USA) were added to the reactor to fix the reaction temperature at 200°C and esterified for two hours. The reaction proceeded and methanol was discharged. At this time, 12 g of tetrabutyl titanate and 10 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of methanol was spilled, 9.45 kg of succinic acid derived from biomass resources (the Netherlands, Reverdia's biosuccinium), and 20 g of the multifunctional compound prepared in Preparation Example 1 were added, and the reaction temperature was fixed at 200°C and water Spilled. At this time, as a catalyst, 12 g of dibutyl tin oxide, 8 g of tetrabutyl titanate, and 15 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was continuously increased, 15 g of antimony trioxide was added as a catalyst, and a condensation polymerization reaction was conducted for 147 minutes under a reduced pressure of 1.5 torr at a temperature of 243°C, and 10 kg of the reaction product obtained through the condensation polymerization reaction 25 g of a carbodiimide compound (Raschig's STABILIZER 9000) was mixed and a chain extension reaction was carried out at 120° C. with a 58 mm diameter twin screw extruder to prepare a functional resin composition using a biomass-derived component.

<Example 8>

Proceeding in the same manner as in Example 7, but a functional resin composition using a biomass-derived component was prepared by using the multifunctional compound prepared through Preparation Example 2.

<Example 9>

A 100 L reactor was replaced with nitrogen, and 18.64 kg of dimethyl terephthalate and 23.43 kg of 1,4-butanediol were added to the reactor, and the reaction temperature was fixed at 200° C., and the esterification was carried out for two hours to discharge methanol. At this time, 10 g of tetrabutyl titanate was added as a catalyst, and 10 g of trimethyl phosphate was added as a stabilizer. After the theoretical amount of methanol was leaked, 11.05 kg of succinic acid derived from biomass resources (the Netherlands, Reverdia's biosuccinium), 1.52 kg of adipic acid (Germany, BASF), and 10 g of the multifunctional compound prepared through Preparation Example 1 were added. After the reaction temperature was fixed to 200 ℃ and water was discharged. At this time, 10 g of dibutyl tin oxide, 10 g of tetrabutyl titanate, and 20 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was continuously increased, 10 g of antimony trioxide was added as a catalyst, and a condensation polymerization reaction was carried out for 162 minutes under a reduced pressure of 1.5 torr at a temperature of 243°C, and 10 kg of the reaction product obtained through the condensation polymerization reaction Ebis-(2,6-diisopropyl-phenylline-2,4-carbodiimide) 25g was mixed and chain extension reaction was carried out at 120℃ with a twin screw extruder with a diameter of 58mm. A functional resin composition was prepared.

<Example 10>

Proceeding in the same manner as in Example 9, a functional resin composition using a biomass-derived component was prepared using the multifunctional compound prepared through Preparation Example 2.

<Comparative Example 1>

A 100 L reactor was replaced with nitrogen, and 18.64 kg of dimethyl terephthalate and 23.43 kg of 1,4-butanediol were added to the reactor, and the reaction temperature was fixed at 200° C., and the esterification was carried out for two hours to discharge methanol. At this time, 10 g of tetrabutyl titanate as a catalyst and 10 g of trimethyl phosphate as a stabilizer were added. After the theoretical amount of methanol was spilled, 12.28 kg of succinic acid derived from biomass resources (Reverdia's biosuccinium, The Netherlands) was added, and the reaction temperature was fixed at 200°C and water was discharged. At this time, as a catalyst, 10 g of dibutyl tin oxide, 10 g of tetrabutyl titanate, and 20 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was continuously increased, 10 g of antimony trioxide was added as a catalyst, and a condensation polymerization reaction was performed for 320 minutes under a reduced pressure of 1.5 torr and a temperature of 243° C. to prepare a resin composition.

<Comparative Example 2>

A 100 L reactor was replaced with nitrogen, and 19.42 kg of dimethyl terephthalate and 23.43 kg of 1,4-butanediol were added to the reactor, the reaction temperature was fixed at 200° C., and the esterification was carried out for two hours to drain methanol. At this time, 10 g of tetrabutyl titanate was added as a catalyst, and 10 g of trimethyl phosphate was added as a stabilizer. After the theoretical amount of methanol was drained, 22.44 kg of succinic acid was added, and the reaction temperature was fixed at 200°C and water was drained. At this time, 10 g of dibutyl tin oxide, 10 g of tetrabutyl titanate, and 20 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was continuously increased, 10 g of antimony trioxide was added as a catalyst, and a condensation polymerization reaction was performed for 200 minutes under a reduced pressure of 1.5 torr and a temperature of 243°C to prepare a resin composition.

<Comparative Example 3>

A 100 L reactor was replaced with nitrogen, and 18.64 kg of dimethyl terephthalate and 23.43 kg of 1,4-butanediol were added to the reactor, and the reaction temperature was fixed at 200° C., and the esterification was carried out for two hours to discharge methanol. At this time, 10 g of tetrabutyl titanate as a catalyst and 10 g of trimethyl phosphate as a stabilizer were added. After the theoretical amount of methanol was drained, 12.28 kg of succinic acid was added, and the reaction temperature was fixed at 200°C and water was drained. At this time, as a catalyst, 10 g of dibutyl tin oxide, 10 g of tetrabutyl titanate, and 20 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was continuously increased, 10 g of antimony trioxide was added as a catalyst, and a condensation polymerization reaction was performed for 192 minutes under a reduced pressure of 1.5 torr and a temperature of 243°C to prepare a resin composition.

<Comparative Example 4>

A 100 L reactor was replaced with nitrogen, and 18.64 kg of dimethyl terephthalate and 23.43 kg of 1,4-butanediol were added to the reactor, the reaction temperature was fixed at 200° C., and the esterification was carried out for two hours to drain methanol. At this time, 10 g of tetrabutyl titanate was added as a catalyst, and 10 g of trimethyl phosphate was added as a stabilizer. After the theoretical amount of methanol was drained, 15.2 kg of adipic acid (Germany, BASF) was added, and the reaction temperature was fixed at 200° C. and water was drained. At this time, as a catalyst, 5 g of dibutyl tin oxide, 15 g of tetrabutyl titanate, and 15 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was continuously increased, 15 g of antimony trioxide was added as a catalyst, and a condensation polymerization reaction was performed for 220 minutes under a reduced pressure of 1.5 torr and a temperature of 243°C to prepare a resin composition.

<Comparative Example 5>

A 100L reactor was replaced with nitrogen, and 23.3 kg of dimethyl terephthalate and 22.53 kg of 1,4-butanediol) were added to the reactor, the reaction temperature was fixed at 200° C., and the esterification was carried out for two hours to drain methanol. At this time, 12 g of tetrabutyl titanate and 10 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of methanol was drained, 11.69 kg of adipic acid (Germany, BASF) was added, and the reaction temperature was fixed at 200° C. and water was drained. At this time, as a catalyst, 12 g of dibutyl tin oxide, 8 g of tetrabutyl titanate, and 15 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was continuously increased, 15 g of antimony trioxide was added as a catalyst, and a condensation polymerization reaction was performed for 196 minutes under a reduced pressure of 1.5 torr at a temperature of 243°C to prepare a resin composition.

The tensile strength, elongation, and biodegradability of the resin compositions prepared through Examples 1 to 8 and Comparative Examples 1 to 5 were measured and shown in Table 1 below.

(However, a film sample having a thickness of 100 μm was prepared using a hot press, and a specimen conforming to the ASTM D638 standard was prepared, but the universal testing machine was used to measure the tensile strength and elongation, and the biodegradability was determined by the above method. The prepared film was cut into widths of 10 cm each, and a specimen was prepared, buried to a depth of 30 cm from the soil surface, and collected 12 months later and measured using a weight reduction method.)

division Tensile strength (kgf/㎠) Elongation(%) Biodegradability (%) Example 1 398 200 79.9 Example 2 401 250 78.8 Example 3 351 675 76.9 Example 4 356 650 75.3 Example 5 412 150 76.4 Example 6 420 150 76.3 Example 7 374 450 56.3 Example 8 381 475 55.1 Example 9 361 475 68.4 Example 10 368 500 70.1 Comparative Example 1 168 75 93.1 Comparative Example 2 378 125 82.7 Comparative Example 3 322 575 80.5 Comparative Example 4 309 450 80.2 Comparative Example 5 367 400 57.3

As shown in Table 1 above, the resin composition prepared through Examples 1 to 10 of the present invention exhibits comparable physical properties to the resin composition prepared through Comparative Examples 1 to 5 and mechanical properties such as tensile strength and elongation Can be seen to improve significantly.

In addition, the number average molecular weight, molecular weight distribution, melting point and melt flow index of the resin compositions prepared through Examples 1 to 10 and Comparative Examples 1 to 5 were measured and shown in Table 2 below.

(However, the number average molecular weight and molecular weight distribution were measured using a gel permeation chromatography analysis method at a temperature of 35°C using an equipment equipped with a column filled with polystyrene. In this case, the developing solvent was chloroform and the concentration of the sample was 5 mg/ mL, the flow rate of the solvent was carried out at a rate of 1.0 mL/min.

In addition, the melting point was measured from 20°C to 200°C at a heating rate of 10°C per minute in a nitrogen atmosphere using a differential scanning calorimeter, and the melt flow index was performed at 190°C and 2,160g according to the standard of ASTM D1238.)

division Number average molecular weight Molecular weight distribution Melting point(℃) Melt flow index (g/10min) Example 1 58,400 3.29 113 3.2 Example 2 68,200 3.37 112 2.6 Example 3 53,200 3.61 126.7 3.6 Example 4 85,900 3.53 128 1.8 Example 5 83,320 3.31 113 2.1 Example 6 89,700 3.42 114 1.4 Example 7 59,998 2.92 169 3.1 Example 8 58,412 2.55 171 3.3 Example 9 56,300 3.21 118 3.2 Example 10 58,280 3.33 118.2 3.4 Comparative Example 1 28,345 3.02 118 4.1 Comparative Example 2 53,112 2.47 108.2 2.5 Comparative Example 3 48,032 2.52 118 5.3 Comparative Example 4 53,312 2.64 126 3.8 Comparative Example 5 57,228 2.42 166 3.5

As shown in Table 2 above, it can be seen that the resin compositions prepared through Examples 1 to 10 of the present invention have a remarkably improved number average molecular weight compared to the resin compositions prepared through Comparative Examples 1 to 5.

Accordingly, the functional resin composition using the biomass-derived component according to the present invention provides a functional resin that is excellent in processability, tear strength, tensile strength, and hydrolysis resistance, thereby suppressing changes over time.

Claims (9)

It consists of biomass-derived succinic acid alone or a mixture of biomass-derived succinic acid and fossil-derived aliphatic dicarboxylic acid, an alcohol mixture, a chain extender and a polyfunctional compound,
The polyfunctional compound is a functional resin composition using a biomass-derived component, characterized in that it is prepared through an esterification reaction of 4,4-bis(4-hydroxyphenyl)valeric acid and polyethylene glycol as shown in [Chemical Formula 1] below. .
[Formula 1]

(Where n is 8 to 10.)
The method according to claim 1,
The composition is a functional resin composition using a biomass-derived component, characterized in that it further comprises an aromatic dicarboxylic acid.
The method according to claim 1 or 2,
The fossil-derived aliphatic dicarboxylic acid is characterized in that it consists of at least one selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, and anhydrides thereof. Functional resin composition using a biomass-derived component.
The method according to claim 2,
The aromatic dicarboxylic acid is a functional resin composition using a biomass-derived component, characterized in that consisting of one or more selected from the group consisting of dimethyl terephthalate, terephthalic acid, isophthalic acid and naphthoic acid.
The method according to claim 1 or 2,
The alcohol mixture is a functional resin composition using a biomass-derived component, characterized in that consisting of at least one selected from the group consisting of biomass-derived 1,4-butanediol and fossil-derived aliphatic diols.
The method of claim 5,
The aliphatic diol derived from the fossil material is at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, neopentyl glycol, propylene glycol, 1,2-butanediol, 1,4-butanediol and 1,6-hexanediol. Functional resin composition using a biomass-derived component, characterized in that consisting of.
The method according to claim 1 or 2,
The chain extender is a functional resin composition using a biomass-derived component, characterized in that consisting of an isocyanate compound or a carbodiimide compound.
delete delete